Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanism

Autores
Sad, Maria Eugenia; Padro, Cristina; Apesteguia, Carlos Rodolfo
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The kinetics and mechanism of coke formation and catalyst deactivation during the synthesis of cresols from phenol methylation were investigated on SiO2–Al2O3, tungstophosphoric acid (HPA) supported on silica, and zeolites HBEA, HZSM5, HMCM22 and HY. The nature, density and strength of surface acid sites were probed by temperature programmed desorption of NH3 coupled with infrared spectra of adsorbed pyridine. Coke formed on the catalysts during reaction was characterized by temperature programmed oxidation. All the samples deactivated on stream. A linear correlation was observed between the initial catalyst deactivation and the amount of coke, thereby indicating that coke formation was responsible for the activity decay. Coking kinetic studies showed that a significant part of coke was rapidly formed from the reactants. When methanol was feeding alone, significant amounts of carbon were formed on the catalysts (between 0.6% and 6.2%C), particularly on samples containing mainly strong Brønsted acid sites. Nevertheless, the coke amounts formed during phenol methylation were clearly higher (between 3.7% and 14.9%C), which showed that phenol was also responsible for coke formation. More insight on the role of phenol and methanol on coke formation was obtained by characterizing the coke nature using infrared spectroscopy. Coked samples recovered after methanol decomposition reaction exhibited IR absorption bands characteristics of olefinic species formed on Brønsted and Lewis acid sites. The IR spectra of coked samples recovered after phenol methylation showed the presence of phenolate, aromatic and polyaromatic species adsorbed mainly on Lewis acid sites.
Fil: Sad, Maria Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Padro, Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Materia
ACID CATALYSTS
COKING KINETICS
COKING MECHANISM
CRESOL SYNTHESIS
PHENOL METHYLATION
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/31608
Acceder
id CONICETDig_4cb3ff80653210808b5a5ea8fa66a347
oai_identifier_str oai:ri.conicet.gov.ar:11336/31608
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanismSad, Maria EugeniaPadro, CristinaApesteguia, Carlos RodolfoACID CATALYSTSCOKING KINETICSCOKING MECHANISMCRESOL SYNTHESISPHENOL METHYLATIONhttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2The kinetics and mechanism of coke formation and catalyst deactivation during the synthesis of cresols from phenol methylation were investigated on SiO2–Al2O3, tungstophosphoric acid (HPA) supported on silica, and zeolites HBEA, HZSM5, HMCM22 and HY. The nature, density and strength of surface acid sites were probed by temperature programmed desorption of NH3 coupled with infrared spectra of adsorbed pyridine. Coke formed on the catalysts during reaction was characterized by temperature programmed oxidation. All the samples deactivated on stream. A linear correlation was observed between the initial catalyst deactivation and the amount of coke, thereby indicating that coke formation was responsible for the activity decay. Coking kinetic studies showed that a significant part of coke was rapidly formed from the reactants. When methanol was feeding alone, significant amounts of carbon were formed on the catalysts (between 0.6% and 6.2%C), particularly on samples containing mainly strong Brønsted acid sites. Nevertheless, the coke amounts formed during phenol methylation were clearly higher (between 3.7% and 14.9%C), which showed that phenol was also responsible for coke formation. More insight on the role of phenol and methanol on coke formation was obtained by characterizing the coke nature using infrared spectroscopy. Coked samples recovered after methanol decomposition reaction exhibited IR absorption bands characteristics of olefinic species formed on Brønsted and Lewis acid sites. The IR spectra of coked samples recovered after phenol methylation showed the presence of phenolate, aromatic and polyaromatic species adsorbed mainly on Lewis acid sites.Fil: Sad, Maria Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Padro, Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaElsevier Science2014-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/31608Sad, Maria Eugenia; Padro, Cristina; Apesteguia, Carlos Rodolfo; Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanism; Elsevier Science; Applied Catalysis A: General; 475; 1-2014; 305-3130926-860XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0926860X14000453info:eu-repo/semantics/altIdentifier/doi/10.1016/j.apcata.2014.01.039info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:20:57Zoai:ri.conicet.gov.ar:11336/31608instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-22 11:20:57.713CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanism
title Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanism
spellingShingle Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanism
Sad, Maria Eugenia
ACID CATALYSTS
COKING KINETICS
COKING MECHANISM
CRESOL SYNTHESIS
PHENOL METHYLATION
title_short Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanism
title_full Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanism
title_fullStr Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanism
title_full_unstemmed Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanism
title_sort Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanism
dc.creator.none.fl_str_mv Sad, Maria Eugenia
Padro, Cristina
Apesteguia, Carlos Rodolfo
author Sad, Maria Eugenia
author_facet Sad, Maria Eugenia
Padro, Cristina
Apesteguia, Carlos Rodolfo
author_role author
author2 Padro, Cristina
Apesteguia, Carlos Rodolfo
author2_role author
author
dc.subject.none.fl_str_mv ACID CATALYSTS
COKING KINETICS
COKING MECHANISM
CRESOL SYNTHESIS
PHENOL METHYLATION
topic ACID CATALYSTS
COKING KINETICS
COKING MECHANISM
CRESOL SYNTHESIS
PHENOL METHYLATION
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv The kinetics and mechanism of coke formation and catalyst deactivation during the synthesis of cresols from phenol methylation were investigated on SiO2–Al2O3, tungstophosphoric acid (HPA) supported on silica, and zeolites HBEA, HZSM5, HMCM22 and HY. The nature, density and strength of surface acid sites were probed by temperature programmed desorption of NH3 coupled with infrared spectra of adsorbed pyridine. Coke formed on the catalysts during reaction was characterized by temperature programmed oxidation. All the samples deactivated on stream. A linear correlation was observed between the initial catalyst deactivation and the amount of coke, thereby indicating that coke formation was responsible for the activity decay. Coking kinetic studies showed that a significant part of coke was rapidly formed from the reactants. When methanol was feeding alone, significant amounts of carbon were formed on the catalysts (between 0.6% and 6.2%C), particularly on samples containing mainly strong Brønsted acid sites. Nevertheless, the coke amounts formed during phenol methylation were clearly higher (between 3.7% and 14.9%C), which showed that phenol was also responsible for coke formation. More insight on the role of phenol and methanol on coke formation was obtained by characterizing the coke nature using infrared spectroscopy. Coked samples recovered after methanol decomposition reaction exhibited IR absorption bands characteristics of olefinic species formed on Brønsted and Lewis acid sites. The IR spectra of coked samples recovered after phenol methylation showed the presence of phenolate, aromatic and polyaromatic species adsorbed mainly on Lewis acid sites.
Fil: Sad, Maria Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Padro, Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
description The kinetics and mechanism of coke formation and catalyst deactivation during the synthesis of cresols from phenol methylation were investigated on SiO2–Al2O3, tungstophosphoric acid (HPA) supported on silica, and zeolites HBEA, HZSM5, HMCM22 and HY. The nature, density and strength of surface acid sites were probed by temperature programmed desorption of NH3 coupled with infrared spectra of adsorbed pyridine. Coke formed on the catalysts during reaction was characterized by temperature programmed oxidation. All the samples deactivated on stream. A linear correlation was observed between the initial catalyst deactivation and the amount of coke, thereby indicating that coke formation was responsible for the activity decay. Coking kinetic studies showed that a significant part of coke was rapidly formed from the reactants. When methanol was feeding alone, significant amounts of carbon were formed on the catalysts (between 0.6% and 6.2%C), particularly on samples containing mainly strong Brønsted acid sites. Nevertheless, the coke amounts formed during phenol methylation were clearly higher (between 3.7% and 14.9%C), which showed that phenol was also responsible for coke formation. More insight on the role of phenol and methanol on coke formation was obtained by characterizing the coke nature using infrared spectroscopy. Coked samples recovered after methanol decomposition reaction exhibited IR absorption bands characteristics of olefinic species formed on Brønsted and Lewis acid sites. The IR spectra of coked samples recovered after phenol methylation showed the presence of phenolate, aromatic and polyaromatic species adsorbed mainly on Lewis acid sites.
publishDate 2014
dc.date.none.fl_str_mv 2014-01
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/31608
Sad, Maria Eugenia; Padro, Cristina; Apesteguia, Carlos Rodolfo; Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanism; Elsevier Science; Applied Catalysis A: General; 475; 1-2014; 305-313
0926-860X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/31608
identifier_str_mv Sad, Maria Eugenia; Padro, Cristina; Apesteguia, Carlos Rodolfo; Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanism; Elsevier Science; Applied Catalysis A: General; 475; 1-2014; 305-313
0926-860X
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0926860X14000453
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.apcata.2014.01.039
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 12.982451

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